CN105103359B - Rechargeable nonaqueous electrolytic battery - Google Patents

Rechargeable nonaqueous electrolytic battery Download PDF

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Publication number
CN105103359B
CN105103359B CN201480018600.9A CN201480018600A CN105103359B CN 105103359 B CN105103359 B CN 105103359B CN 201480018600 A CN201480018600 A CN 201480018600A CN 105103359 B CN105103359 B CN 105103359B
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active material
material layer
electrode active
barrier film
nonaqueous electrolytic
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CN105103359A (en
Inventor
萩山康介
本田崇
山口隆太
松崎生马
宫本健史
岛村修
松本圭佑
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Nissan Motor Co Ltd
Envision AESC Japan Ltd
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Nissan Motor Co Ltd
Automotive Energy Supply Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0468—Compression means for stacks of electrodes and separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Battery Mounting, Suspending (AREA)

Abstract

[problem] provides a kind of can be effectively discharged out the gas of generation in the binding agent using water-based binder as negative electrode active material outside electrode and even if the decline of battery capacity also few rechargeable nonaqueous electrolytic battery is used for a long time.A kind of [solution] rechargeable nonaqueous electrolytic battery, it has generating element, and the generating element is included：Positive pole, it is formed with positive electrode active material layer on the surface of positive electrode collector；Negative pole, it is formed with the negative electrode active material layer comprising water-based binder on the surface of negative electrode collector；And barrier film, it is configured between aforementioned positive electrode active material layer and negative electrode active material layer, and the density of negative electrode active material layer is 1.4~1.6g/cm3At least one layer of electrolyte layer is configured with negative electrode active material layer and aforementioned positive electrode active material layer between foregoing barrier film, relative to the gross thickness of aforementioned positive electrode, foregoing negative pole, foregoing barrier film and aforementioned electrolyte layer, the ratio of the gross thickness of aforementioned positive electrode, foregoing negative pole and foregoing barrier film is for 0.85 less than 1.0.

Description

Rechargeable nonaqueous electrolytic battery
Technical field
The present invention relates to rechargeable nonaqueous electrolytic battery.
Background technology
In recent years, using the surging as background of environmental protection movement, electric automobile (EV), hybrid electric are being carried out The exploitation of automobile (HEV) and fuel-cell vehicle (FCV).As their engine driving power supply, discharge and recharge can be repeated Secondary cell is adapted to, and particularly can expect the rechargeable nonaqueous electrolytic batteries such as high power capacity, high-power lithium rechargeable battery Get most of the attention.
Rechargeable nonaqueous electrolytic battery has to be formed includes positive active material (such as LiCoO on collector surface2、 LiMnO2、LiNiO2Deng) positive electrode active material layer.Formed in addition, rechargeable nonaqueous electrolytic battery has on collector surface Include negative electrode active material (metal and its oxidation such as carbonaceous material, Sn, Si such as lithium metal, coke and natural/Delanium Thing material etc.) negative electrode active material layer.
The binding agent bonded for the active material for making to use in active material layer is divided into organic solvent system binding agent (in water In do not dissolve/scattered, dissolution/dispersion in organic solvent binding agent) and water-based binder (dissolution/dispersion is viscous in water Tie agent).On organic solvent system binding agent, fee of material in organic solvent, reclaim take, cost wholesale in terms of waste treatment Expense, it is sometimes industrial unfavorable.On the other hand, on water-based binder, the supply as the water of raw material is easy, in addition, Tool has the advantage that：What is produced when drying is vapor, therefore, it is possible to significantly inhibit the equipment investment to production line, can be realized The reduction of carrying capacity of environment.Water-based binder, which also has, to be had the advantage that：With organic solvent system binder phase ratio, even if being bonded to be a small amount of Effect is also big, it is possible to increase the active material ratio per same volume, can make electrode high capacity.
Due to having the advantage that, carry out using water-based binder as the binding agent for forming active material layer to come Form the various trials of negative pole.For example, disclosing a kind of secondary electricity of nonaqueous electrolyte in Japanese Unexamined Patent Publication 2010-80297 publications Pond negative pole, its in negative electrode active material layer contain as the latex system binding agents such as the butadiene-styrene rubber (SBR) of water-based binder, And polyvinyl alcohol and carboxymethyl cellulose.
The content of the invention
But, it is known that in comprising the rechargeable nonaqueous electrolytic battery using the negative electrode active material layer of water-based binder, Compared with using the situation of organic system binding agent, the gas quantitative change produced during first discharge and recharge by electrode is more.If the gas produced Quantitative change is more, then worries to impact battery behavior, when battery particularly is used for a long time, and there is a situation where battery capacity decline.
Therefore, it is an object of the present invention to provide a kind of using water-based binder as the viscous of negative electrode active material layer The gas of generation can be effectively discharged out during knot agent outside electrode, it is also few non-aqueous even if the decline that battery capacity is used for a long time Electrolyte secondary battery.
The rechargeable nonaqueous electrolytic battery of the present invention is included：Positive pole, it is formed with positive pole work on the surface of positive electrode collector Property material layer；Negative pole, it is formed with the negative electrode active material layer comprising water-based binder on the surface of negative electrode collector；With every Film, it is configured between aforementioned positive electrode active material layer and negative electrode active material layer.Moreover, with following characteristics：Negative pole The density of active material layer is 1.4~1.6g/cm3, relative to positive pole, negative pole, barrier film and aforementioned electrolyte layer gross thickness, just The ratio of the gross thickness of pole, negative pole and barrier film is 0.85 less than 1.0.
Brief description of the drawings
Fig. 1 is the basic structure of the aqueous electrolyte lithium ion secondary batteries for the non-dipole type for showing platypelloid type (cascade type) Schematic cross-section.
Fig. 2A is the schematic diagram of the rechargeable nonaqueous electrolytic battery of the suitable embodiment as the present invention.
Fig. 2 B are the direction view from the A directions in Fig. 2A.
Fig. 3 is that other the suitable embodiments for being shown as the present invention include rechargeable nonaqueous electrolytic battery The stereogram of battery component.
Embodiment
The present invention is a kind of rechargeable nonaqueous electrolytic battery, and it has generating element, and the generating element is included：Positive pole, It is formed with positive electrode active material layer on the surface of positive electrode collector；Negative pole, it is formed with the surface of negative electrode collector and included The negative electrode active material layer of water-based binder；And barrier film, it is configured between positive electrode active material layer and negative electrode active material layer, The density of negative electrode active material layer is 1.4~1.6g/cm3, in negative electrode active material layer and positive electrode active material layer at least One layer is configured with electrolyte layer between barrier film, relative to the gross thickness of positive pole, negative pole, barrier film and electrolyte layer, positive pole, negative pole And the ratio of the gross thickness of barrier film is 0.85 less than 1.0.
As described previously for water-based binder, water can be used as solvent during manufacture active material layer, therefore exist Various advantages, and it is also high to bond the cohesive force of active material.But, the present inventor etc. has found, if in negative electrode active material layer , then compared with using the negative pole of organic solvent system binding agent, there is gas production during first discharge and recharge in middle use water-based binder The problem of life amount is how such.It is thought that because：The water of the solvent used when water-based binder is dissolved into (scattered) remains in electricity It is extremely interior, the water decomposition and form gas, therefore with organic solvent system binder phase ratio, the generation of gas becomes many.Due to such The generation of gas, in the case of using water-based binder in negative electrode active material layer, battery when battery is used for a long time is put Declined compared with the discharge capacity of battery of the capacitance when initial.It is thought that because：Due to the generation of gas, activity The formation of SEI overlay films in residual gas on material layer, negative terminal surface becomes uneven.
For each single cell units capacity be people's livelihood purposes several times~tens times of cascade type laminated cell, in order to Energy density is improved, electrode is maximized, and therefore, the yield of gas becomes much larger, and then the uneven reaction on negative pole Become easily generation.
Had made intensive studies based on above-mentioned discovery, as a result produce following ideas：If made in negative electrode active material layer Make the path of gas, make the mechanism being discharged to the gas deviate from out of active material layer outside generating element, then will can produce Raw gas is effectively discharged out outside system, so as to complete the solution of the present invention.In the present invention, negative electrode active material layer it is close The thickness of degree and electrolyte layer (being located between negative pole (positive pole) active material layer/barrier film) is in specific scope.Think by suitable The density of degree control negative electrode active material layer, forms the path of the gas produced, and then by there is electrolyte layer, from the member that generates electricity The gas of the path abjection of gas in part is discharged to outside generating element system from electrolyte layer.During in the absence of electrolyte layer, Gas will be discharged from barrier film, active material layer, but barrier film, active material layer are resin bed.With gas from such resin bed Discharge compare, the discharge of gas from liquid faster, therefore, compared with existing battery, according to the solution of the present invention, Neng Gouyou Effect it is exhausted.That is, the solution of the present invention is：By the path and electrode surface of the electrode vertical direction for suitably making gas The path in direction, the gas of generation is smoothly discharged out outside system, improves battery performance.
Therefore, according to the present invention, even in use water-based binder as negative electrode active material layer binding agent when, produce Gas be also easy to be released to outside electrode, therefore, even if the decline of battery capacity also few nonaqueous electrolyte two is used for a long time Primary cell is also possibly realized.
Hereinafter, as the preferred embodiment of rechargeable nonaqueous electrolytic battery, for the secondary electricity of non-aqueous electrolyte lithium ion Pond is illustrated, it is not limited to following embodiment.
It should be noted that marking same symbol to identity element in the description of the drawings, repeat specification is omitted.In addition, For convenience of explanation, the dimensional ratios of accompanying drawing are exaggerated, sometimes different from actual ratio.
Fig. 1 be the non-dipole type for schematically showing platypelloid type (cascade type) aqueous electrolyte lithium ion secondary batteries (with The schematic cross-section of basic structure down also referred to as " laminate type battery ").As shown in figure 1, the cascade type electricity of present embodiment There is the substantially rectangular generating element 21 for actually carrying out discharge and recharge reaction to be encapsulated in outside the battery as shell body in pond 10 The structure of the inside of shell material 29.Herein, generating element 21 has the structure for stacking gradually positive pole, barrier film 17 and negative pole. In addition, barrier film 17 is built-in with nonaqueous electrolyte (such as liquid electrolyte).Just having the two sides configuration in positive electrode collector 11 There is the structure of positive electrode active material layer 13.Negative pole has is configured with negative electrode active material layer 15 on the two sides of negative electrode collector 12 Structure.Specifically, 1 positive electrode active material layer 13 and negative electrode active material layer 15 adjacent thereto is made to clip the phase of barrier film 17 It is right, it is sequentially laminated with negative pole, dielectric substrate and positive pole.
It should be noted that on two outermost outermost layer positive electrode collectors of generating element 21, only in one side It is configured with positive electrode active material layer 13, but it is also possible to which active material layer is set on two sides.That is, can also will be active on two sides The collector of material layer is used directly as outermost collector, and only active material layer is provided with most in one side without being made The special collector of outer layer.Alternatively, it is also possible to by making the configuration of positive pole and negative pole be overturned with Fig. 1, so that outermost layer negative pole Collector is located at two outermost layers of generating element 21, and the one or two sides made in the outermost layer negative electrode collector is configured with negative pole work Property material layer.
Positive electrode collector 11 and negative electrode collector 12 have following structures：It is separately installed with and each electrode (positive pole and negative pole) The positive pole current collections plate (piece) 25 and negative electrode collector plate (piece) 27 of conducting, make it be clipped in the end of property material for battery shell 29, and export To the outside of property material for battery shell 29.Positive pole current collections plate 25 and negative electrode collector plate 27 respectively can be as needed via positive wires And negative wire (not shown) is installed in the positive electrode collector 11 and negative pole of each electrode by ultrasonic bonding, resistance welding etc. Collector 12.
In Fig. 1, between negative electrode active material layer 15 and barrier film 17 and between positive electrode active material layer 13 and barrier film 17 There is electrolyte layer 16.
It should be noted that showing the laminate type battery of the non-dipole type of platypelloid type (cascade type) in Fig. 1, but it is also possible to For the bipolar cell comprising bipolar electrode, the bipolar electrode, which has, to be electrically coupled in the positive-active of the one side of collector Material layer and it is electrically coupled in the negative electrode active material layer in the face of the opposite side of collector.In this case, a collector is held a concurrent post Positive electrode collector and negative electrode collector.
Hereinafter, for the electrolyte layer and negative electrode active material layer of the characteristic as the present invention, further specifically It is bright.
[electrolyte layer]
In the present invention, relative to the gross thickness of positive pole, negative pole, barrier film and electrolyte layer, the total thickness of positive pole, negative pole and barrier film The ratio of degree is 0.85 less than 1.0.Herein, electrolyte layer is simply by the presence of in any active material layer in generating element And just it is enough between barrier film, but in view of the effect of the present invention, then deposited preferably at least between negative electrode active material layer and barrier film In electrolyte layer.More preferably there is electrolyte layer between positive electrode active material layer and negative electrode active material layer and barrier film. Relative to the gross thickness of positive pole, negative pole, barrier film and electrolyte layer, the ratio of the gross thickness of positive pole, negative pole and barrier film is less than 0.85 When, the path of lithium ion is elongated, hinders the ion movement in battery.Therefore, reaction becomes uneven in electrode surface, in electrode Inside locally lie in the high part of gas generated many, voltage.In addition, the ratio of the gross thickness of positive pole, negative pole and barrier film be 1.0 with When upper, the resin bed of barrier film etc. is compressed and is discharged gas, and discharge of the gas to outside system becomes unable to be smoothed out.Cause This, relative to the gross thickness of positive pole, negative pole, barrier film and electrolyte layer, the ratio of the gross thickness of positive pole, negative pole and barrier film is 1.0 During above or less than 0.85, the long-term cycle characteristics of battery declines.In addition, being played from further as gas discharge originally Set out in terms of The effect of invention, relative to the gross thickness of positive pole, negative pole, barrier film and electrolyte layer, positive pole, negative pole and barrier film The ratio of gross thickness is preferably 0.95 less than 1.0.
Hereinafter, the gross thickness of positive pole, negative pole, barrier film and electrolyte layer is also referred to as to the thickness of electrification structure element.In addition, The gross thickness of positive pole, negative pole and barrier film is also referred to as to the thickness of generating element component.It should be noted that generating element component Thickness is obtained by the physical thickness of positive pole, negative pole and barrier film by calculating.Moreover, the thickness of electrification structure element is obtained i.e. as follows Can：The thickness for the battery that measure is encapsulated with laminated film, obtains the thickness of generating element obtained from subtracting the thickness of laminated film.
It should be noted that electrolyte layer refers to what is be made up of the liquid electrolyte for being dissolved with lithium salts in organic solvent Layer, it is meant that there is the thickness being made up of liquid electrolyte between barrier film and active material layer.In other words, " in active material Layer barrier film between be configured with electrolyte layer " refer to active material layer do not contacted physically with barrier film, active material layer and every The state filled up between film by electrolyte with certain thickness.Therefore, electrolyte " layer " does not mean only that the physical envelope in end The structure closed, as long as there is the thickness being made up of liquid electrolyte between barrier film and active material layer with regard to it is enough.
Constituting the liquid electrolyte of electrolyte layer has the form for being dissolved with lithium salts in organic solvent.Liquid electrolyte has There is the function of the carrier as lithium ion.As the organic solvent used, for example, it can exemplify ethylene carbonate (EC), carbonic acid The carbonates such as sub- propyl ester (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate.In addition, being used as lithium Salt, can equally use Li (CF3SO2)2N、Li(C2F5SO2)2N、LiPF6、LiBF4、LiClO4、LiAsF6、LiTaF6、LiCF3SO3 Etc. the compound that can be added in the active material layer of electrode.Liquid electrolyte further can contain in addition to mentioned component Additive.As the concrete example of such compound, can for example enumerate vinylene carbonate, methyl vinylene, Carbonic acid dimethyl vinylene, carbonate vinylene, dipheryl carbonate base vinylene, carbonic acid ethyl vinylene, carbonic acid Diethyl vinylene, vinyl ethylene carbonate, carbonic acid 1,2- divinyl ethyl, carbonic acid 1- methyl isophthalic acids-vinyl are sub- Ethyl ester, carbonic acid 1- methyl -2- vinyl ethyl, carbonic acid 1- ethyl -1- vinyl ethyl, carbonic acid 1- ethyl -2- vinyl Ethyl, ethylene alkenyl vinylene, allyl ethyl, ethylene carbonate epoxide methyl ethyl, allyl oxygen Ylmethyl ethyl, propylene carbonate pivaloyloxymethyl ethyl, methyl propylene pivaloyloxymethyl ethyl, carbonic acid acetenyl Ethyl, carbonic acid propargyl ethyl, ethylene alkynyloxy group methyl ethyl, carbonic acid propynyloxy base ethyl, carbonic acid methylene Ethyl, carbonic acid 1,1- dimethyl -2- methylene ethyls etc..Wherein, the preferred sub- ethene of vinylene carbonate, methyl Ester, vinyl ethylene carbonate, more preferably vinylene carbonate, vinyl ethylene carbonate.These ring type carbonic esters can be with 1 kind is only used alone, two or more can also be applied in combination to use.
These electrolyte can be independent a kind, can also combine two or more.
For electrolyte layer, described in manufacture method as be described hereinafter like that, by barrier film and electrode layer poststack, injection is superfluous Electrolyte, thus between barrier film and the active material layer of electrode formed.
The method of the thickness of electrolyte layer is controlled to be not particularly limited, a suitable embodiment is that control puts on electricity Group pressure (the group pressure of pond element；Japanese：Group pressure) method.Therefore, a suitable embodiment party of the invention The group pressure that formula is applied to generating element is 0.07~0.7kgf/cm2The secondary electricity of nonaqueous electrolyte of (6.86~68.6kPa) Pond.More appropriately, the group pressure for putting on generating element is 0.08~0.7kgf/cm2(7.84~49.0kPa).Herein, group pressure The strong external force for referring to put on generating element, group pressure can use diaphragm pressure distribution measurement system to be easily determined, this In specification, using the value for using Tekscan, the diaphragm pressure distribution measurement system of Inc. manufactures and determining.
The control of group pressure is not particularly limited, can be to generating element physically directly or indirectly additional external force, control The external force is made, thus control group pressure.As the applying method of such external force, preferably use and shell body application pressure is added Press component.That is, a suitable embodiment of the invention is a kind of rechargeable nonaqueous electrolytic battery, and it, which has, utilizes shell body By the structure that generating element is closed, also with pressing element, the pressing element is turned into the group pressure for putting on generating element 0.07~0.7kgf/cm2Mode to shell body apply pressure.
Fig. 2A is the schematic diagram of the rechargeable nonaqueous electrolytic battery of other suitable embodiments as the present invention, Fig. 2 B are the direction views from the A directions in Fig. 2A.Being sealed with the shell body 1 of generating element has the flat of oblong-shaped Shape, the electrode slice 4 for taking out electric power is drawn from its sidepiece.Generating element is wrapped up by battery case body, is heated around it Connect, generating element is sealed in the state of electrode slice 4 to be led to outside.Herein, generating element is equivalent to before illustrating The generating element 21 of lithium rechargeable battery 10 shown in Fig. 1.In Fig. 2,2 are denoted as the SUS plates of pressing element, and 3 represent to make Electrode slice (negative plate or positive plate) is represented for the stationary fixture of fixing component, 4.Pressing element is in order to first to put on generating The group pressure of part turns into 0.07~0.7kgf/cm2Mode be controlled and configure.As pressing element, it can enumerate poly- The elastomeric materials such as urethane sheet rubber, aluminium, SUS etc. metallic plate etc..In addition, can constantly be assigned to generating element from pressing element Set out in terms of giving constant pressure, preferably further with the fixing component for fixing pressing element.In addition, passing through regulation Fixation of the stationary fixture to pressing element, can easily control to put on the group pressure of generating element.
It should be noted that the taking-up on the piece shown in Fig. 2, is also not particularly limited.It can be drawn just from both sides Pole piece and negative plate, positive plate and negative plate can also be respectively classified into it is multiple and from each side take out etc., however it is not limited to shown in Fig. 2 Situation.
Fig. 3 is that other the suitable embodiments for being shown as the present invention include rechargeable nonaqueous electrolytic battery The stereogram of battery component.Battery component 120 has：Monocell 130, it is stacked with multiple generating members encapsulated by shell body Part；Housing 122, it includes the lower house 123 for forming box shape and the upper shell 124 for forming cap-shaped shape.The edge of upper shell 124 Portion is rolled tightly in the edge part of the perisporium of lower house 123 by ca(u)lk processing, with jut prominent in the stacking direction 125.In Fig. 3 mode, pressing element is housing 122, and housing 122 also holds a concurrent post fixing component.Battery pack described in Fig. 3 In part, due to having determined that battery accommodates the size of the thickness of housing, so applying to accommodating the generating element after storehouse (stack) Group pressure depend on accommodate housing thickness.Therefore, for the control for the group pressure for putting on generating element, by considering electricity The thickness of pond storehouse, regulating cell accommodates the thickness of housing, so as to control.In which, rechargeable nonaqueous electrolytic battery Constituted by the generating element (monocell) encapsulated by shell body and as the housing of pressing element.
Lower house 123 and upper shell 124 than relatively thin steel plate or aluminium sheet by forming.The metal materials such as steel, aluminium due to Good rigidity, so being able to ensure that rigidity, and realizes miniaturization and low noise, further, since with good Thermal conductivity, so by improving cooling performance and temperature control, low consumption and long lifetime can be realized.
There are sleeve 126 and monocell 130 in the inner containment of housing 122.Sleeve 126 is configured at 4 angles of housing 122, Played a role as the stiffener of housing 122, in order to bear to use for fastening the fastening force of cell stack.128 represent It is arranged on the padded coaming between monocell 130 and upper shell 124.
In addition, can be in the battery receiving as pressing element and fixing component as rechargeable nonaqueous electrolytic battery The form of battery (monocell) is accommodated in housing, the battery (monocell) is with battery case bodies such as metal can, laminated films Obtained from encapsulation generating element.
[negative electrode active material layer]
In the present invention, the density for making negative electrode active material layer is 1.4~1.6g/cm3.If the density of negative electrode active material layer More than 1.6g/cm3, then the density of active material layer is high, and therefore, the gas of generation will not be deviate from out of electrode, and long-term circulation is special Property decline.If in addition, the density of negative electrode active material layer is less than 1.4g/cm3, then the connective decline of active material, electronics electricity Conductance declines, therefore battery performance declines.From the further effect aspect for playing the present invention, negative electrode active material layer Density is preferably 1.4~1.55g/cm3。
In order to by the density domination of negative electrode active material layer within the above range, can by suitably adjust manufacture electrode when Pressing pressure is controlled.It should be noted that the density of negative electrode active material layer represents the active material layer matter of per unit volume Amount.Specifically, it can obtain as follows：Negative electrode active material layer is taken out from battery, solvent present in electrolyte etc. etc. is removed Afterwards, by long side, short side, highly obtain electrode volume, after the weight for determining active material layer, with weight divided by volume, thus may be used To obtain.
Negative electrode active material layer includes negative electrode active material.As negative electrode active material, for example, graphite (graphite), the carbon material such as soft carbon, hard carbon, lithium-compound transition metal oxide (such as Li4Ti5O12), metal material, lithium Alloy system negative material etc..According to circumstances, negative electrode active material of more than two kinds can be applied in combination.From capacity, power characteristic Viewpoint is set out, and preferably uses carbon material or lithium-compound transition metal oxide as negative electrode active material.Need explanation Be, naturally it is also possible to use negative electrode active material than that described above.
The average grain diameter of each active material included in negative electrode active material layer is not particularly limited, but from high power Viewpoint is set out, preferably 1~100 μm, more preferably 1~30 μm.
Water-based binder is comprised at least in negative electrode active material layer.On water-based binder, due to the water as raw material Supply is easy, and produced when drying is vapor, thus with the equipment investment that can be significantly inhibited to production line, can Realize the advantage of the reduction of carrying capacity of environment.
Water-based binder refers to using water as solvent or the binding agent of decentralized medium, specifically, equivalent to thermoplastic resin Fat, the polymer with caoutchouc elasticity, water soluble polymer etc. or their mixture.Herein, decentralized medium is used as using water Binding agent includes showing as latex or all categories of emulsion, refers to occur emulsification or the polymer being suspended in water, example with water Polymer emulsion class obtained from emulsion polymerization is carried out in the system as can enumerate in self-emulsifying.
As water-based binder, polystyrene macromolecule (SBR styrene butadiene rubberses, styrene-second can be specifically enumerated Vinyl acetate copolymer, styrene acrylic copolymers etc.), acrylonitrile-butadiene rubber, methyl methacrylate-fourth two Alkene rubber, (methyl) acrylic polymer (polyethyl acrylate, polyethyl methacrylate, polyacrylic acid propyl ester, poly- methyl Methyl acrylate (methyl methacrylate rubber), polypropylmethacryla,es, polyacrylic acid isopropyl ester, polymethylacrylic acid are different The own ester of propyl ester, butyl polyacrylate, polybutyl methacrylate, polyacrylic acid, the own ester of polymethylacrylic acid, polyacrylic acid ethyl Own ester, polymethylacrylic acid ethylhexyl, polyacrylic acid lauryl, polylauryl methacrylate etc.), it is polytetrafluoroethylene (PTFE), poly- Ethene, polypropylene, ethylene-propylene copolymer, polybutadiene, butyl rubber, fluorubber, PEO, Hydrin, Polyphosphazene, polyacrylonitrile, polystyrene, ethylene-propylene-diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, polyester Resin, phenolic resin, epoxy resin；Polyvinyl alcohol (average degree of polymerization is preferably 200~4000, and more preferably 1000~3000, Saponification degree is preferably 80 moles of more than %, more preferably 90 moles more than %) and its modified body (Ethylene/vinyl acetate=2/ 1~80 mole of % in the vinyl acetate unit of the copolymer of 98~30/70 mol ratios is saponified, polyvinyl alcohol 1~50 Mole % parts acetal compound etc.), it is starch and its modified body (oxidized starch, organic phosphate starch, cationic starch etc.), fine Tie up plain derivative (carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and their salt etc.), gather Vinyl pyrrolidone, polyacrylic acid (salt), polyethylene glycol, the copolymerization of (methyl) acrylamide and/or (methyl) acrylates Thing [(methyl) acrylamide polymer, (methyl) acrylamide-(methyl) acrylate copolymer, (methyl) acrylic acid alkyl (carbon number 1~4) ester-(methyl) acrylate copolymer etc.], styrene-maleic acid salt copolymer, the Mannich of polyacrylamide Modified body, formaldehyde condensation type resin (urea-formaldehyde resin, melamine formaldehyde resin etc.), polyamide polyamines or dialkyl group Amine-epoxy chloropropane copolymer, polyethyleneimine, casein, soybean protein, synthetic proteins and galactomannans derive Water soluble polymers such as thing etc..These water-based binders can be used singly or in combination of two or more to use.
From the viewpoint of caking property, above-mentioned water-based binder is preferably comprised selected from by SBR styrene butadiene rubberses, propylene At least 1 in the group of nitrile-butadiene rubber, methyl methacrylate butadiene rubber and methyl methacrylate rubber composition Plant rubber series binding agent.And then, from the good aspect of caking property, water-based binder preferably comprises styrene-butadiene rubber Glue.
During using SBR styrene butadiene rubberses as water-based binder, from the viewpoint of coating raising, preferred compositions Use above-mentioned water soluble polymer.It is used as the water soluble polymer for being adapted to be applied in combination with SBR styrene butadiene rubberses, Ke Yiju Go out polyvinyl alcohol and its modified body, starch and its modified body, cellulose derivative (carboxymethyl cellulose, methylcellulose, hydroxyl second Base cellulose and their salt etc.), PVP, polyacrylic acid (salt) or polyethylene glycol.Wherein, as bonding Agent, preferably combines SBR styrene butadiene rubberses and carboxymethyl cellulose.SBR styrene butadiene rubberses and water soluble polymer Be not particularly limited containing mass ratio, optimization styrene-butadiene rubber：Water soluble polymer=1：0.3~0.7.
In binding agent used in negative electrode active material layer, the content of water-based binder is preferably 80~100 mass %, excellent Elect 90~100 mass %, preferably 100 mass % as.As the binding agent beyond water-based binder, following positive poles can be enumerated Binding agent used in active material layer.
As long as the binder amount included in negative electrode active material layer is the amount that can bond active material, just do not have special Limitation, relative to active material layer, preferably 0.5~15 mass %, more preferably 1~10 mass %, more preferably 2~ 4 mass %.Water-based binder is high due to cohesive force, therefore with organic solvent system binder phase than that can be formed with a small amount of addition Active material layer.Accordingly, with respect to active material layer, content of the binding agent in active material layer is preferably 0.5~15 matter Measure %, more preferably more preferably 1~10 mass %, 2~4 mass %.
As needed, also containing conductive auxiliary agent, electrolyte, (polymer substrate, ionic conductivity gather negative electrode active material layer Compound, electrolyte etc.), other additives such as lithium salts for improving ionic conductivity.
Conductive auxiliary agent refer in order to improve the electric conductivity of positive electrode active material layer or negative electrode active material layer and adding for being compounded Plus thing.As conductive auxiliary agent, the carbon materials such as the carbon blacks such as acetylene black, graphite, carbon fiber can be enumerated.Active material layer contains conduction During auxiliary agent, the electric network of the inside of active material layer is effectively formed, the raising of the power characteristic of battery is can help to.
As electrolytic salt (lithium salts), Li (C can be enumerated2F5SO2)2N、LiPF6、LiBF4、LiClO4、LiAsF6、 LiCF3SO3Deng.
As ion-conducting polymers, for example, PEO (PEO) system and PPOX (PPO) system Polymer.
The mix ratio of the composition included in negative electrode active material layer and positive electrode active material layer described later is not particularly limited. For mix ratio, it can be adjusted by appropriate reference on the known knowledge of lithium rechargeable battery.For each work Property material layer thickness it is not also specifically limited, can be suitably with reference to the existing known knowledge on battery.If enumerating one, The thickness of each active material layer is 2~100 μm or so.
[positive electrode active material layer]
Positive electrode active material layer includes active material, as needed also comprising conductive auxiliary agent, binding agent, electrolyte (polymerization Thing matrix, ion-conducting polymers, electrolyte etc.), other additives such as lithium salts for improving ionic conductivity.
Positive electrode active material layer includes positive active material.As positive active material, for example, it can enumerate LiMn2O4、 LiCoO2、LiNiO2、Li(Ni-Mn-Co)O2And a part for these transition metal by other elements replace obtained by material etc. Lithium-compound transition metal oxide, lithium-transition metal phosphate compound, lithium-transition metal sulphate etc..According to circumstances, Positive active material of more than two kinds can be applied in combination.From the viewpoint of capacity, power characteristic, lithium-transition gold is preferably used Category composite oxides are used as positive active material.More preferably use Li (Ni-Mn-Co) O2And a part of quilt of these transition metal Material (hereinafter also referred to as " NMC composite oxides ") obtained from other elements displacement.NMC composite oxides have lithium atom Layer and transition metal (Mn, Ni and Co order are properly configured) atomic layer clip the stratiform crystalline substance that oxygen atomic layer is alternately laminated Body structure, the transition metal M relative to every 1 atom includes 1 Li atom, and the Li amounts that can be taken out turn into the lithium manganese oxidation of spinelle system 2 times, i.e. supply capacity of thing turns into 2 times, can have high power capacity.
What the part that NMC composite oxides also include transition metal as described above had been replaced by other metallic elements Composite oxides.As other elements in this case, can enumerate Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, Fe, B, Ga, In, Si, Mo, Y, Sn, V, Cu, Ag, Zn etc., preferably Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, more preferably Ti, Zr, P, Al, Mg, Cr, from the viewpoint of cycle characteristics raising, more preferably Ti, Zr, Al, Mg, Cr.
From the high aspect of theoretical discharge capacity, NMC composite oxides preferably have formula (1)： LiaNibMncCodMxO2(wherein, in formula, a, b, c, d, x meet 0.9≤a≤1.2,0<b<1、0<c≤0.5、0<d≤0.5、0≤ X≤0.3, b+c+d=1.M is at least one kind of in the element selected from Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr) shown in Composition.Herein, a represents Li atomic ratio, and b represents Ni atomic ratio, and c represents Mn atomic ratio, and d represents Co atomic ratio, x tables Show M atomic ratio.From the viewpoint of cycle characteristics, 0.4≤b≤0.6 preferably in formula (1).It should be noted that each member The composition of element can be for example measured by inductively coupled plasma (ICP) emission spectrometry.
As a rule, from the viewpoint of the purity and raising electronic conductivity for improving material, it is known that nickel (Ni), cobalt (Co) And manganese (Mn) contributes to capacity and power characteristic.Ti etc. is the element of the transition metal in aliquot replacement lattice.From cycle characteristics From the viewpoint of, preferably a part for transition elements is replaced by other metallic elements, particularly preferably 0 in formula (1)<x≤ 0.3.Think by least one kind of generation solid solution in the group being made up of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr and Cr, So as to crystal structure it is stabilized, therefore as a result, even if repeat discharge and recharge can also prevent the capacity of battery from declining, can realize Excellent cycle characteristics.
As preferred embodiment, from the viewpoint of the harmony for improving capacity and life characteristic, preferably logical B, c and d are 0.44≤b≤0.51,0.27≤c≤0.31,0.19≤d≤0.26 in formula (1).It should be noted that certainly may be used To use positive active material than that described above.
The average grain diameter of each active material included in positive electrode active material layer is not particularly limited, from the sight of high power Point sets out, preferably 1~100 μm, more preferably 1~20 μm.
As the binding agent used in positive electrode active material layer, it is not particularly limited, for example, can enumerates following material.Can To enumerate polyethylene, polypropylene, polyethylene terephthalate (PET), polyethers nitrile, polyacrylonitrile, polyimides, polyamides Amine, cellulose, carboxymethyl cellulose (CMC) and its salt, vinyl-vinyl acetate copolymer, polyvinyl chloride, styrene fourth two Alkene rubber (SBR), isoprene rubber, butadiene rubber, ethylene propylene rubber, propylene diene copolymer, benzene Ethylene butadiene styrene block copolymer and its hydride, styrene-isoprene-styrene block copolymer and The thermal plastic high polymers such as its hydride, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE) (PTFE), tetrafluoroethene hexafluoropropene Copolymer (FEP), tetrafluoroethene perfluoroalkyl vinyl ether copolymer (PFA), ethylene tetrafluoroethylene copolymer (ETFE), Fluororesin, inclined two such as polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF) PVF-hexafluoropropene system fluorubber (VDF-HFP systems fluorubber), vinylidene fluoride-hexafluoropropene-tetrafluoroethene system fluorubber (VDF-HFP-TFE systems fluorubber), vinylidene fluoride-pentafluoropropene system fluorubber (VDF-PFP systems fluorubber), inclined difluoro second Alkene-pentafluoropropene-tetrafluoroethene system fluorubber (VDF-PFP-TFE systems fluorubber), vinylidene fluoride-perfluoromethylvinyl base Ether-tetrafluoroethene system fluorubber (VDF-PFMVE-TFE systems fluorubber), vinylidene fluoride-chlorotrifluoroethylene system fluorubber (VDF- CTFE systems fluorubber) etc. vinylidene fluoride fluorubber, epoxy resin etc..These binding agents can be used alone, can also group Conjunction uses two or more.
As long as the amount that the binder amount included in positive electrode active material layer can bond active material, just without special Limit, relative to active material layer, more preferably preferably 0.5~15 mass %, 1~10 mass %.
On other additives beyond binding agent, it can use and the above-mentioned column identical thing of negative electrode active material layer one Matter.
[barrier film]
Barrier film, which has, keeps electrolyte so that it is guaranteed that function and the conduct of lithium-ion-conducting between positive pole and negative pole The function of partition wall between positive pole and negative pole.
As barrier film, it is not particularly limited, can suitably utilizes existing known barrier film.For example, can enumerate by absorbing Keep the polymer of above-mentioned electrolyte and/or barrier film, the nonwoven cloth diaphragm of fibroplastic porous piece etc..
As the barrier film by polymer and/or fibroplastic porous piece, for example, it can use micro-porous (micro- porous Film).As the specific form by the polymer and/or fibroplastic porous piece, for example, it can enumerate by following substances Micro-porous (micro-porous film) barrier film formed：The polyolefin such as polyethylene (PE), polypropylene (PP)；Laminated multi-layer said polyolefins Obtained from layered product (such as being made the PP/PE/PP layered product of 3-tier architecture), polyimides, aramid fiber, gather inclined difluoro second Hydrocarbon system resin, the glass fibres such as alkene-hexafluoropropene (PVdF-HFP) etc..
It is different according to use as the thickness of micro-porous (micro-porous film) barrier film, therefore can not entirely provide. If providing 1, in the engine of electric automobile (EV), mixed power electric car (HEV), fuel cell car (FCV) etc. In the purposes such as driving secondary cell, it is generally desirable to single or multiple lift and for 4~60 μm.Foregoing micro-porous (micro-porous film) every It is preferable that the fine aperture of film, which is less than 1 μm (being usually tens nm or so aperture) to the maximum,.
As nonwoven cloth diaphragm, cotton, artificial silk, acetate, nylon, polyester is used alone or as a mixture；The polyenes such as PP, PE Hydrocarbon；The existing known material such as polyimides, aramid fiber.As long as in addition, the bulk density of non-woven fabrics can utilize infiltrated height Molecular gel electrolyte obtains sufficient battery behavior, is not particularly limited.And then, as long as the thickness of nonwoven cloth diaphragm with Dielectric substrate is identical, preferably 5~200 μm, particularly preferably 10~100 μm.
In addition, can be the barrier film that heat-resistant insulating layer is laminated with porous matrix as barrier film.Heat-resistant insulating layer is bag Ceramic layer containing inorganic particle and binding agent.By the way that with heat-resistant insulating layer, the inside of the barrier film increased when temperature rises should Power is relaxed, therefore, it is possible to obtain thermal contraction inhibition.In addition, by with heat-resistant insulating layer, with heat-resistant insulating layer The mechanical strength of barrier film is improved, and is not susceptible to the rupture of membranes of barrier film.And then, due to thermal contraction inhibition and high mechanical strength, institute It is not flexible with manufacturing process's septation in electrical equipment.
In addition, as described above, barrier film includes electrolyte.As electrolyte, as long as such function can be played, just do not have Especially limitation, can use liquid electrolyte or gel polymer electrolyte.For liquid electrolyte, above-mentioned electrolysis can be enumerated The liquid electrolyte used in liquid layer.
Gel polymer electrolyte has in the matrix polymer (main polymer) comprising ion-conducting polymers It is injected with the structure of aforesaid liquid electrolyte.By using gel polymer electrolyte as electrolyte, there is no stream for electrolyte Dynamic property is excellent in terms of becoming easily to interdict the ionic conductivity of each interlayer.As matrix polymer (mass polymerization Thing) ion-conducting polymers, can for example enumerate PEO (PEO), PPOX (PPO) and they be total to Polymers etc..The electrolytic salts such as lithium salts can be well dissolved in such polyalkylene oxide based polymer.
The matrix polymer of gel electrolyte can show excellent mechanical strength by forming cross-linked structure.For shape Into cross-linked structure, appropriate polymerization initiator can be used, to the polymerizable polymer of polyelectrolyte formation (for example PEO, PPO) implement the polymerizations such as thermal polymerization, polymerizable ultraviolet, radiation polymerization, electron beam polymerization processing.
[battery case body]
As battery case body 29, known metal tank shell can be used, in addition, can use can cover hair Electric device, the bag-shaped housing that has used the laminated film containing aluminium.For the laminated film, for example, it can use and stack gradually PP, aluminium, the laminated film of 3-tier architecture formed by nylon etc., but not by its any limitation.It is excellent from high power, cooling performance Large scale equipment that is different, being suitable for EV, HEV is set out with viewpoint as battery, it is generally desirable to laminated film.In addition, from energy Enough easily adjust from it is outside put on the group pressure of generating element, be easily tailored as desired electrolyte layer thickness in terms of Set out, shell body is more preferably the laminated film for including aluminium.
Volume of the internal volume of shell body preferably than generating element is big.Herein, the internal volume of shell body refers to use shell body It is after encapsulation, be sucked by vacuum before shell body in volume.In addition, the volume of generating element refers to generating element space The volume of shared part, includes the hole portion in generating element.Volume by the interior volume specific ratio generating element of shell body is big, So as to which the volume of gas can be stored when there is gas generation.Therefore, it is possible to successfully carry out discharge of the gas to outside system, production Influence of the raw gas to battery behavior is small, and battery behavior is improved.In addition, when producing gas, by existing in shell body internal memory The remainder of gas can be stored, the volume of generating element can be kept constant, therefore, it is possible to make interelectrode distance permanent The fixed, reaction of continuous uniform.The internal volume of shell body is preferably capable storing the size of certain level of gas, specifically, Preferably, the 0.03 of the volume in addition to hole portion of the big generating element of volume of the interior volume specific ratio generating element of shell body~ 0.12 volume.
In mobile applications etc., the battery of maximization is required recently.Moreover, outer for the gas of generation is effectively discharged out Effect of the invention as portion, in the case of gas generated many area batteries, can more effectively play the effect. Therefore, in the present invention, from the meaning for the effect for more effectively playing the present invention, preferably with shell body covering generating element Into battery structure to be large-scale.Specifically, negative electrode active material layer is rectangular-shaped, and the length of the rectangular-shaped short side is preferred For more than 100mm.So large-scale battery can be used for vehicular applications.The upper limit of the length of rectangular-shaped short side is not limited especially Determine, usually below 250mm.
In addition, as the viewpoint of the large-scale electrochemical cell different from the viewpoint of the physical size of electrode, can also be by battery face Product, the maximization of the relationship specifications battery of battery capacity.For example, in the case of flat cascade type laminated cell, in cell area (maximum of the projected area of the battery comprising battery case body) is 5cm relative to the ratio of rated capacity2/ more than Ah and Rated capacity is in more than 3Ah battery, the cell area of per unit capacity is big, therefore, gas generated still many.Therefore, The water-based binders such as SBR are used for the battery performance of the battery of the formation of the negative electrode active material layer (longevity after especially long-term circulation Order characteristic) decline it is such the problem of it is easily more obvious.Therefore, in the advantage for showing generation by action effect of the invention more The rechargeable nonaqueous electrolytic battery of big aspect, preferably the manner is the battery of maximization as described above.And then, it is rectangular-shaped The length-width ratio of electrode is preferably 1~3, and more preferably 1~2.It should be noted that the length-width ratio of electrode is used as rectangular-shaped positive pole The aspect ratio of active material layer and be defined.By making length-width ratio be such scope, it is necessary to use this hair of water-based binder There are following advantages in bright：Become able to equably discharge gas in face direction, can further suppress uneven overlay film Generation.
[collector]
The material for constituting collector is not particularly limited that it is preferable to use metal.Specifically, can be with as metal Enumerate aluminium, nickel, iron, stainless steel, titanium, copper and alloy etc..In addition it is preferable to use the clad material of nickel and aluminium, copper With the coating material of the combination of the clad material of aluminium or these metals etc..Furthermore it is possible to be formed in metal surface aluminium coating Paper tinsel.Wherein, from the viewpoint of electronic conductivity, battery operating potential, preferably aluminium, stainless steel, copper.
The size of collector is determined according to the use of battery.If for example, for requiring the large-scale of high-energy-density Battery, then can be with the big collector of usable floor area.It is not particularly limited for the thickness of collector.The thickness of collector is usual For 1~100 μm or so.
[positive pole current collections plate and negative electrode collector plate]
The material for constituting collector plate (25,27) is not particularly limited, and can use and be used currently as lithium rechargeable battery The known high conductivity material that uses of collector plate.As the constituent material of collector plate, preferably such as aluminium, copper, titanium, nickel, no Become rusty the metal materials such as steel (SUS), their alloy.From the viewpoint of light weight, corrosion resistance, high conductivity, more preferably aluminium, Copper, particularly preferably aluminium.It should be noted that for positive pole current collections plate 25 and negative electrode collector plate 27, identical material can be used Material, can also use different materials.
[positive wire and negative wire]
In addition, though omit diagram, but can via positive wire, negative wire by collector 11 and collector plate (25, 27) electrically connected between., can be equally using known lithium ion secondary electricity as positive wire and the constituent material of negative wire The material used in pond.It should be noted that being covered from the part that shell takes out preferably by heat-shrinkable tube of high temperature insulation etc. Lid so that will not be contacted with ancillary equipment, wiring etc. and leak electricity or made to product (such as automobile component, especially electronic equipment) Into influence.
[manufacture method]
Manufacture method for rechargeable nonaqueous electrolytic battery is not particularly limited, and is referred in the manufacture field of battery Existing known knowledge is manufactured.
A suitable embodiment for the manufacture method of the rechargeable nonaqueous electrolytic battery of the present invention is as follows.
A kind of manufacture method of rechargeable nonaqueous electrolytic battery, it includes following process：Formed barrier film, negative pole and just The process for the layered product that pole is laminated；The layered product is sealing into the process in shell body；Electrolysis is injected into the shell body The process of liquid；Pressing element is configured with the shell body, is turned into the group pressure that generating element is put in foregoing shell body 0.07~0.7kgf/cm2Mode to shell body apply pressure process.
Hereinafter, each operation is briefly described.
(1) process for forming the layered product for being laminated barrier film, negative pole and positive pole
First, the slurry comprising active material is coated on collector, dries it, make electrode.Now, negative electrode active Material layer uses water-based binder, therefore preferably uses aqueous slurry.When making aqueous slurry, water solvent can be used. Water solvent is compared with the situation using organic solvent, it is not necessary to large-scale production equipment, therefore excellent in terms of productivity ratio Choosing, in addition, in terms of environmental protection it is also preferred that.Water solvent refers to the mixed solvent of water and water and organic solvent.Specifically, may be used To enumerate water, water and methanol, ethanol or the mixed solvent of ethyl acetate, more preferably water.Use water and a small amount of organic solvent When mixed solvent is as water solvent, mixed solvent is integrally set to 100 mass %, the content of the water of the in the mixed solvent is preferred For 80~99.9 mass %, more preferably 90~99.5 mass %.
Then, the electrode and barrier film of above-mentioned making are laminated with desired form and stacking number, made as generating The layered product of element.
(2) process that layered product is encapsulated with shell body
Then, the piece being connected in the outermost layer engagement of the layered product obtained using the above method with lead, is revealed with the lead Go out to outside mode and encapsulate cell device.At this point it is possible to be provided for injecting the open end of electrolyte.
(3) process of electrolyte is injected into shell body
As the method that electrolyte is injected in shell body, it can enumerate：The interelectrode hole of normal direction is injected using decompression The method that electrolyte is injected in portion；Method in above-mentioned shell body and being packaged etc. is together injected the electrolyte into layered product.
(4) pressing element is configured on shell body, is turned into the group pressure that generating element is put in foregoing shell body 0.07~0.7kgf/cm2Mode to shell body apply pressure process
It is not particularly limited, for example, can be enumerated using the method for pressing element to additional group of pressure of shell body：As described above Pressing element is fixed with stationary fixture to method of generating element application group pressure etc. shown in Fig. 2.
[battery pack]
Multiple monocells can be connected or battery pack is made in electric component.Specifically, battery pack using at least two with It is upper, by series connectionization or parallel connectionization or both and constitute., being capable of free pondage and electricity by carrying out series, parallel Pressure.
Can also by battery connect or be connected in parallel it is multiple, formed can assembly and disassembly small-sized battery pack.Moreover, Can by this can the small-sized battery pack of assembly and disassembly further connect multiple in series or in parallel, formation is suitable for the high body of requirement Product energy density, the vehicle traction power supply of high volumetric power density, accessory power supply, with Large Copacity, powerful battery Group.Battery pack, several sections of compact battery groups of this outer stack are made on to connect several batteries to make the battery pack of Large Copacity, Determined according to the battery capacity of the vehicle (electric automobile) of carrying, power.
[vehicle]
Above-mentioned rechargeable nonaqueous electrolytic battery can also maintain discharge capacity even if long-term use, and cycle characteristics is good.In electricity In the vehicular applications such as electrical automobile, mixed power electric car, fuel-cell vehicle, hybrid power fuel cell car, with electrically/shifting Dynamic electronics applications are compared, it is desirable to high power capacity, maximization, while needing long lifetime.Therefore, above-mentioned nonaqueous electrolyte is secondary Battery can for example be suitable for vehicle traction power supply, accessory power supply as motor vehicle power supply.
Specifically, battery pack can be equipped on vehicle.In the present invention, due to long-term reliability and power can be constituted The battery of the high life of excellent, therefore, if carrying such battery, can constitute the plug-in mixing of EV travel distance length The electric automobile of power electric automobile, the traveling distance that once charges.Because, by by battery or the multiple batteries of combination The battery pack of formation be used for such as automobile in hybrid electric vehicle, fuel-cell vehicle, electric automobile (including carriage (car, The commercial car such as truck, bus, kart etc.) and cart (motorcycle), tricycle), as the high life and reliably The high automobile of property.But, purposes is not limited to automobile, the moving body such as being readily applicable to other vehicle, such as electric cars Various power supplys, the mounting power utilization such as uninterruptible power supply can also be used as.
Embodiment
Hereinafter, further it is described in detail using embodiment and comparative example, but the present invention is not limited in following reality Apply example.
(embodiment 1)
1. the making of electrolyte
By ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) mixed solvent (30：30：40 (volume ratio)) it is used as solvent.In addition, by 1.0M LiPF6It is used as lithium salts.And then, relative to above-mentioned solvent and above-mentioned lithium salts Total 100 mass % add 2 mass % vinylene carbonate, make electrolyte.It should be noted that " 1.0M LiPF6” Refer to the lithium salts (LiPF in the mixture of the mixed solvent and lithium salts6) concentration be 1.0M.
2. the making of positive pole
Prepare comprising the LiMn as positive active material2O4(average grain diameter：15 μm) 85 mass %, it is used as conductive auxiliary agent The mass % of acetylene black 5 and PVdF10 mass % as binding agent solid constituent.It is appropriate relative to solid constituent addition The METHYLPYRROLIDONE (NMP) of solvent is adjusted as slurry viscosity, anode sizing agent is made.Then, anode sizing agent is coated with In the two sides of the aluminium foil (20 μm) as collector, it is dried/suppresses, makes one side coated weight 20.0mg/cm2, two sides it is thick The positive pole of 172 μm of degree (including paper tinsel).In addition, the density of positive electrode active material layer is 2.92g/cm3。
3. the making of negative pole
Prepare comprising the Delanium (average grain diameter as negative electrode active material：20 μm) 95 mass %, help as conduction The mass % of acetylene black 2 of agent and SBR (Japanese Zeon Corporation are manufactured) 2 mass %, CMC as binding agent (NIPPON PAPER Chemicals CO., LTD. manufactures, trade name：SUNROSE) 1 mass % solid constituent.Relative to The appropriate ion exchange water that solvent is adjusted as slurry viscosity of solid constituent addition, makes cathode size.Then, negative pole is starched Material is coated on the two sides of the copper foil (15 μm) as collector, is dried/suppresses, and makes one side coated weight 5.64mg/cm2、 The negative pole of two 92 μm of face thicknesses (including paper tinsel).In addition, the density of negative electrode active material layer is 1.46g/cm3。
4. the completion process of monocell
The positive pole of above-mentioned making is cut into 210 × 184mm oblong-shaped, negative electrode layer is cut into the rectangular of 215 × 188mm Shape (rectangular-shaped) (15, positive pole, 16, negative pole).The positive pole and negative pole is clipped 219 × 191mm barrier film, (polyolefin is micro- more Pore membrane, 25 μm of thickness, porosity 55%) alternately it is laminated.
Electrode slice is respectively welded on these positive poles and negative pole, with the electrolyte of the amount described in table 1 be together sealed in by In the shell of aluminium lamination press mold formation, battery is completed, the big polyurethane rubber piece (thickness 3mm) of specific electrode surface and then Al is utilized Plate (thickness 5mm) clamps battery, is pressurizeed in the way of as the group pressure described in table 1, thus completes monocell.So The rated capacity of the battery of making is 17.7Ah, and cell area is 28.8cm relative to the ratio between rated capacity2/Ah.Need explanation , the rated capacity of battery (monocell) obtains as follows.
On rated capacity, for testing battery, after injection electrolyte, place 10 hours or so, initially filled Electricity.Then, at 25 DEG C of temperature, in 3.0V~4.15V voltage range, it is measured by following step 1~5.
Step 1：Reached after 4.15V, stopped 5 minutes using 0.2C constant-current charge.
Step 2：After step 1, using constant-voltage charge charge within 1.5 hours, stop 5 minutes.
Step 3：Reached by 0.2C constant-current discharge after 3.0V, using constant voltage discharge discharge within 2 hours, then stop 10 seconds.
Step 4：Reached by 0.2C constant-current charge after 4.1V, using constant-voltage charge charge within 2.5 hours, then Stop 10 seconds.
Step 5：Reached by 0.2C constant-current discharge after 3.0V, using constant voltage discharge discharge within 2 hours, then stop 10 seconds.
Rated capacity：By discharge capacity (the CCCV electric discharge appearances from constant-current discharge into the electric discharge of constant voltage discharge in step 5 Amount) it is used as rated capacity.
The positive pole of obtained monocell, negative pole, the gross thickness (thickness of electrification structure element) of barrier film and electrolyte layer, just Ratio (generating element component of the gross thickness of pole, negative pole and barrier film relative to the gross thickness of positive pole, negative pole, barrier film and electrolyte layer Thickness/electrification structure element thickness ratio) be recorded in table 1.
(embodiment 2~12 and comparative example 1~3)
Electrolyte is injected according to the electrolyte content described in table 1, and with as the shell body group pressure described in table 1 Mode is pressurizeed, in addition, is operated similarly to Example 1, so as to make battery.
(evaluation of battery)
1. the primary charging process of monocell
The rechargeable nonaqueous electrolytic battery (monocell) made as described above by charge-discharge performance test evaluation.For this Charge-discharge performance is tested, and is kept for 24 hours in 25 DEG C of thermostat is remained, and implements primary charging.For primary charging, with Then 0.05CA current value constant-current charge (CC) is amounted to 25 hours to 4.2V with constant pressure (CV) charging.Then, 40 are being remained DEG C thermostat in keep 96 hours.Then, it is discharged in 25 DEG C of thermostat is remained, with 1C current rate 2.5V, then setting 10 minutes stop time.
2. the evaluation of battery
The rechargeable nonaqueous electrolytic battery (monocell) made as described above by charge-discharge performance test evaluation.For this Charge-discharge performance is tested, in 45 DEG C of thermostat is remained, and makes battery temperature after 45 DEG C, to make a service test.For filling Electricity, with 1C current rate constant-current charge (CC) to 4.2V, is then amounted to 2.5 hours with constant pressure (CV) charging.Then, 10 are set After stop time minute, carry out being discharged to 2.5V with 1C current rate, then the stop time of 10 minutes is set.As 1 circulation, implements charge and discharge electric test.Discharge capacity is used as appearance relative to the ratio of first discharge capacity after 300 are circulated Measure sustainment rate.Show the result in table 1.
[table 1]
The thickness of ﹡ electrification structure elements：Positive pole, negative pole, the gross thickness of barrier film and electrolyte layer
The thickness of generating element component：The gross thickness of positive pole, negative pole and barrier film
From the above results, the battery of embodiment 1~9 is compared with the battery of comparative example 1~3, the appearance after long-term circulation Measure sustainment rate high.
The Japanese patent application No. 2013-064911 that the application was filed an application based on March 26th, 2013, reference is simultaneously whole Body introduces the disclosure of which.
Description of reference numerals
1 shell body for being sealed with generating element,
2 pressing elements,
3 fixing components,
4 electrode slices,
10 lithium rechargeable batteries,
11 positive electrode collectors,
12 negative electrode collectors,
13 positive electrode active material layers,
15 negative electrode active material layers,
16 electrolyte layers,
17 barrier films,
21 generating elements,
25 positive pole current collections plates,
27 negative electrode collector plates,
29 battery case bodies,
120 battery components,
122 housings,
123 lower houses,
124 upper shells,
125 juts,
126 sleeves,
128 padded coamings,
130 monocells.

Claims (11)

1. a kind of rechargeable nonaqueous electrolytic battery, it has generating element, and the generating element is included：
Positive pole, it is formed with positive electrode active material layer on the surface of positive electrode collector；
Negative pole, it is formed with the negative electrode active material layer comprising water-based binder on the surface of negative electrode collector；With
Barrier film, it is configured between the positive electrode active material layer and the negative electrode active material layer,
The density of the negative electrode active material layer is 1.4~1.6g/cm3,
It is configured between at least one layer of and described barrier film in the negative electrode active material layer and the positive electrode active material layer The electrolyte layer being made up of liquid electrolyte, it is total relative to the positive pole, the negative pole, the barrier film and the electrolyte layer Thickness, the ratio of the gross thickness of the positive pole, the negative pole and the barrier film is for 0.85 less than 1.0.
2. rechargeable nonaqueous electrolytic battery according to claim 1, wherein, relative to the positive pole, negative pole, described The gross thickness of barrier film and the electrolyte layer, the ratio of the gross thickness of the positive pole, the negative pole and the barrier film for 0.95 with Above and less than 1.0.
3. rechargeable nonaqueous electrolytic battery according to claim 1 or 2, it, which has, utilizes shell body by the generating element Closed structure, also with the group pressure to put on the generating element as 0.07~0.7kgf/cm2Mode to shell Body applies stressed pressing element.
4. rechargeable nonaqueous electrolytic battery according to claim 1 or 2, it, which has, utilizes shell body by the generating element Closed structure, the volume of the interior volume specific ratio generating element of shell body is big.
5. rechargeable nonaqueous electrolytic battery according to claim 1 or 2, wherein, the negative electrode active material layer is rectangle Shape, the length of the rectangular-shaped short side is more than 100mm.
6. rechargeable nonaqueous electrolytic battery according to claim 1 or 2, wherein, cell area is relative to rated capacity Ratio is 5cm2/ more than Ah, and rated capacity is more than 3Ah, and the cell area is the battery comprising battery case body Projected area.
7. rechargeable nonaqueous electrolytic battery according to claim 1 or 2, wherein, it is used as rectangular-shaped positive active material The aspect ratio of layer and the length-width ratio of electrode that is defined is 1~3.
8. rechargeable nonaqueous electrolytic battery according to claim 4, wherein, the shell body is the laminated film comprising aluminium.
9. rechargeable nonaqueous electrolytic battery according to claim 1 or 2, it, which has, utilizes shell body by the generating element Closed structure, also with the group pressure to put on the generating element as 0.07~0.7kgf/cm2Mode to shell Body applies stressed pressing element, also with the fixing component for the fixed holding pressing element.
10. rechargeable nonaqueous electrolytic battery according to claim 1 or 2, wherein, the water-based binder include be selected from by SBR styrene butadiene rubberses, acrylonitrile-butadiene rubber, methyl methacrylate butadiene rubber and methyl methacrylate At least one kind of rubber series binding agent in the group of ester rubber composition.
11. rechargeable nonaqueous electrolytic battery according to claim 10, wherein, the water-based binder comprising styrene- Butadiene rubber.
CN201480018600.9A 2013-03-26 2014-03-26 Rechargeable nonaqueous electrolytic battery Active CN105103359B (en)

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